Iodine → N-(4-Iodopyridin-3-yl)-2,2-dimethylpropanamide

HRID 422096

반응식

HRID 422096 반응식
[CH3:1][C:2]([CH3:13])([CH3:12])[C:3]([NH:5][C:6]1[CH:7]=[N:8][CH:9]=[CH:10][CH:11]=1)=[O:4].NCCCCN.C([Li])CCC.[I:25]I.[NH4+].[Cl-]>C(OCC)C>[I:25][C:11]1[CH:10]=[CH:9][N:8]=[CH:7][C:6]=1[NH:5][C:3](=[O:4])[C:2]([CH3:13])([CH3:12])[CH3:1]

참가 물질

7

반응물 5

HCID 807IodineHCID 1045PutrescineHCID 25517Ammonium ChlorideHCID 46550442,2-dimethyl-N-(pyridin-3-yl)propanamideHCID 178418339Butyllithium

생성물 1

HCID 10447729N-(4-Iodopyridin-3-yl)-2,2-dimethylpropanamide수율 23.3%

시약·촉매·용매 1

HCID 3283Diethyl Ether용매

반응 조건

온도
-13 °C

실험 절차

Equip a 250 mL 3-neck round bottom flask with: a magnetic stirrer, a thermocouple, a dry ice/acetone bath, a nitrogen atmosphere, and an addition funnel. Charge 2,2-dimethyl-N-pyridin-3-yl-propionamide (3.0 g, 16.8 mmol), diethyl ether (67 mL), tetramethylene diamine (4.68 g, 6.08 mL, 40.3 mmol). Cool the reaction to −78° C. Add slowly via glass syringe n-butyllithium (2.5 M solution in hexane, 16.2 mL, 40.3 mmol) over 10 min. Allow the reaction to warm to −13° C. over 2 hours. Cool the reaction to −78° C. Add an iodine solution (8.5 g, 33.6 mmol in 20 mL THF) to the reaction via the addition funnel and mix 2.5 hours at −68° C. Quench the reaction by the addition of saturated aqueous NH4Cl solution (40 mL). Extract with ethyl acetate (100 mL) and discard the aqueous phase. Wash the organic layer with a saturated aqueous sodium thiosulfate solution (100 mL) and saturated aqueous sodium chloride. Dry the organic phase over sodium sulfate and filter. Concentrate in vacuo to give brown oil. Chromatograph on silica (80 g) eluting with a gradient of 100% dichloromethane to 70% ethyl acetate/30% dichloromethane to afford the title compound (1.19 g, 23%). MS (ES) m/z 305 [M+1]+

후처리

  1. customEquip a 250 mL 3-neck round bottom flask with: a magnetic stirrer
  2. temperatureCool
  3. customthe reaction to −78° C
  4. customthe reaction
  5. temperatureCool
  6. customthe reaction to −78° C
  7. customto the reaction via the addition funnel
  8. additionmix 2.5 hours at −68° C
  9. customQuench
  10. customthe reaction
  11. extractionExtract with ethyl acetate (100 mL)
  12. washWash the organic layer with a saturated aqueous sodium thiosulfate solution (100 mL) and saturated aqueous sodium chloride
  13. dry with materialDry the organic phase over sodium sulfate
  14. filtrationfilter
  15. concentrationConcentrate in vacuo
  16. customto give brown oil
  17. washChromatograph on silica (80 g) eluting with a gradient of 100% dichloromethane to 70% ethyl acetate/30% dichloromethane

출처 및 근거

ORD 기록
ord-af6df10f30894d27aab6aed98815b222
출처 데이터셋
uspto-grants-2012_01
특허 번호
US08101628B2

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